We noted that the tunneling-percolation framework is quite well understood at the extreme cases of percolationlike and hoppinglike behaviors but that the intermediate regime has not been previously discussed, in spite of its relevance to the intensively studied electrical properties of nanocomposites. Following that we study here the conductivity of dispersions of particle fillers inside an insulating matrix by taking into account explicitly the filler particle shapes and the interparticle electron-tunneling process. We show that the main features of the filler dependencies of the nanocomposite conductivity can be reproduced without introducing any a priori imposed cutoff in the interparticle conductances, as usually done in the percolationlike interpretation of these systems. Furthermore, we demonstrate that our numerical results are fully reproduced by the critical path method, which is generalized here in order to include the particle filler shapes. By exploiting this method, we provide simple analytical formulas for the composite conductivity valid for many regimes of interest. The validity of our formulation is assessed by reinterpreting existing experimental results on nanotube, nanofiber, nanosheet, and nanosphere composites and by extracting the characteristic tunneling decay length, which is found to be within the expected range of its values. These results are concluded then to be not only useful for the understanding of the intermediate regime but also for tailoring the electrical properties of nanocomposites.

Here, we show that the conductivity of conductor-insulator composites in which electrons can tunnel from each conducting particle to all others may display both percolation and tunneling (i.e. hopping) regimes depending on few characteristics of the composite. Specifically, we find that the relevant parameters that give rise to one regime or the other are $D/\xi$ (where $D$ is the size of the conducting particles and $\xi$ is the tunneling length) and the specific composite microstructure. For large values of $D/\xi$, percolation arises when the composite microstructure can be modeled as a regular lattice that is fractionally occupied by conducting particle, while the tunneling regime is always obtained for equilibrium distributions of conducting particles in a continuum insulating matrix. As $D/\xi$ decreases the percolating behavior of the conductivity of lattice-like composites gradually crosses over to the tunneling-like regime characterizing particle dispersions in the continuum. For $D/\xi$ values lower than $D/\xi\simeq 5$ the conductivity has tunneling-like behavior independent of the specific microstructure of the composite.Comment: 8 pages, 5 figure

We present an in-depth analysis of the geometrical percolation behavior in the continuum of random assemblies of hard oblate ellipsoids of revolution. Simulations were carried out by considering a broad range of aspect ratios, from spheres up to aspect-ratio-100 platelike objects, and with various limiting two-particle interaction distances, from 0.05 times the major axis up to 4.0 times the major axis. We confirm the widely reported trend of a consistent lowering of the hard particle critical volume fraction with increase of the aspect ratio. Moreover, by assimilating the limiting interaction distance to a shell of constant thickness surrounding the ellipsoids, we propose a simple relation based on the total excluded volume of these objects which allows us to estimate the critical concentration from a quantity that is quasi-invariant over a large spectrum of limiting interaction distances. Excluded volume and volume quantities are derived explicitly.

We report on our Monte Carlo calculations of the conductivity of monosized and conducting spherical particles dispersed in a homogeneous matrix, with interparticle transport mechanism given by electron tunneling. We show that our numerical results can be reproduced by a simple formula based on a critical path analysis and which gives also a practical way to estimate the characteristic tunneling length ξ in real composites. We find that ξ is about 1 nm for several low structure carbon black polymer composites, in agreement with the expected order of magnitude.